Certain polyepoxide treated amine modified thermoplastic phenol-aldehyde resins and method of making same



' include monoepoxides.

United States Patent CERTAIN POLYEPOXIDE TREATED AMINE MODI- FIED THERMOPLASTIC PHENOL-ALDEHYDE RESINS AND METHOD OF MAKING SAME Melvin De Groote, St. Louis, and Kwan-Ting Shen, Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware 14 Claims. (Cl. 260-45) The present invention is a continuation-in-part of our co-pending application, Serial No. 305,079 filed August 18, 1952, now abandoned, and a division of our copending application Serial No. 338,576, filed February 24, 1953.

Our invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. Our invention is also concerned with the application of such chemical products or compounds in various other arts and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification.

The products of our invention are obtained by the method of first condensing certain phenol-aldehyde resins, hereinafter described in detail, with certain basic hydroxylated polyamines, hereinafter described in detail, and formaldehyde, which condensation is followed by reaction of the resin condensate with certain phenolic polyepoxides, also hereinafter described in detail, and cogenerically associated compounds formed in the preparation of the polyepoxides.

In preparing diepoxides or the low molal polymers one does usually obtain cogeneric materials which may However, the cogeneric mixture is invariably characterized by the fact that there is on the average, based on the molecular weight, of course, more than one epoxide group per molecule.

A more limited aspect of the invention is represented by the reaction product of (A) an amine modified phenolaldehyde resin condensate as described, and (B) a member of the class of (1') compounds of the following formula:

and (2) cogenerically associated compounds formed in the preparation of (1) preceding.

It so happens that the bulk of information concerned with the preparation of compounds having two oxirane rings appears in the patent literature and for the most part in the recent patent literature. Thus, in the subsequent text, there are numerous references to such patents for purpose of supplying information and also for purpose of brevity.

Notwithstanding presented in considerable detail, yet the description becomes somewhat involved and certain facts should be kept in mind. The epoxides, and particularly the diepoxides 2,828,277, Patented Mar, 25, 1958 may have no connecting bridge between the phenolic nuclei as in the case of a diphenyl derivative or may have a variety of connecting bridges, i. e., divalent linking radicals. Our preference is that either diphenyl compounds be employed or else compounds Where the divalent link is obtained by the removal of a carbonyl oxygen atom as derived from a ketone or aldehyde.

If it were not for the expense involved in preparing and purifying the monomer we would prefer it to any other form, i. e., in preference to the polymer or mixture of polymer and monomer.

Stated another way we would prefer to use materials of the kind described, for example, in U. S. Patent 2,530,353, dated November 14, 1950. Said patent describes compounds having the general formula wherein R is an aliphatic hydrocarbon bridge, each n independently has one of the values 0 and 1, and X is an alkyl radical containing from 1 to 4 carbon atoms.

The list of patents hereinafter referred to in the text as far as polyepoxide goes is as follows:

U. S. Patent No. Dated Inventor July 5, 1938 Schafer. December 13, 1938 Mikeska et al. September 26, 1939.-.. g0.

April 2, 1940".--

July 16,

June 3, 1941. June 17, 1941 June 9, 1942--." October 12, 1943 November 4, 1947- December 28, 1948 February 15, 1949 do 0.

September 27, 1949.-- Dietzler. November 15, 1949-.. Mikeska et a1.

- Dietzler et al.

Book et a1. Bender et al. Stevens et al.

' Do. Dietzler.

January 8, 1952 -I rln January 22, 1952 The compounds having two oxirane rings and employed for combination with the reactive amine-modified phenol-aldehyde resin condensates as herein described are compounds of the following formula and cogenerithe fact that subsequent data will be cally associated compounds formed in their preparation:

in which R represents a divalent radical selected from the class of ketone residues formed by the elimination of the ketonic oxygen atom and aldehyde residuesobtained by the elimination of the aldehydic oxygen atom, the divalent radical H H -o-og I H H' the divalent radical, the divalentsulfone radical, and the divalent monosulfide radical S, the divalent radical and the divalent disulfide radical S-S; and R is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and. a nuclear hydrogen atom from the phenol in which R, R", and R'" represent a member of the class of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; n represents an integer selected from the class of zero and 1, and n represents a whole number not greater than 3. The above mentioned compounds and those cogenerically associated compounds formed in their preparation are thermoplastic and organic solventsoluble. Reference to being thermoplastic characterizes them as being'liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus diflferentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents, such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference condensate) pound containing-the epoxy rings before reacting with'the amine-modifiedresin. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as for example, kerosene, benzene, toluene, dioxane, various ketones, chlorinated solvents, dibutyl ether dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimethoxy tetraethyleneglycol, i i

The expression epoxy" is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring issomettmes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the ,word epoxy unless indicated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2- epoxide rings or oxirane rings in the alpha-omega position. This is a departure, of course, from the standpoint of strictly formal nomenclature as in theexample of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy{3,4-epoxybutane (1,2-3,4 diepoxybutane). 1 Y

It well may be that even though the previously suggested formula represents the principal component, or

components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex-resinous .epoxldes which arepolyeth'er derivatives of poly- 4 hydric phenols containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. See U. S. Patent No. 2,494,295, dated January 10, 1950, to Greenlee. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not insoluble resins and have certain solubility characteristics not inherent in the usual thermosetting resins. Note, for example, that said U. S. Patent No. 2,494,295 describes products wherein the epoxide derivative can combine with a sulfonamide resin. The intention in said U. S. Patent 2,494,295, of course, is to obtain ultimately a suitable resinous product having the characteristics of a comparatively insoluble resin.

Having obtained a reactant'having generally 2 epoxy rings as depicted in the last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any amine-modified phenol-aldehyde resin by virtue of the fact that there are always present reactive hydroxyl groups which'are part of the'phenolic nuclei and there may be present reactive hydrogen atoms attached to a nitrogen atom, or an oxygen atom, depending on the .presence'of a hydroxylated group or secondary amino group.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a'mole of the oxyalkylating agent, i. e., the compound having two oxirane rings and an amine condensate. Proceeding with the example previously described'it is obvious the reaction ratio of twov .as follows:

in which the various characters have their previous significance and the characterization condensate is simply an abbreviation for the condensate which is described in greater detail subsequently.

Such final product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, or for that matter, a solution of Water containing an acid such as'hydrochloric acid, acetic acid, hydroxyace'tic acid, etc. In other words, the nitrogen groups present, Whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with water) or a salt form such as the acetate, chloride, etc. The purpose in this-instance is to difierentiate from insoluble resinous materials, particularly thoseresulting from gelation or cross-linking. Not only does this property serve to differentiate from instances where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distinctly dis'persible in 5% gluconic acid. For instance, the products, freed from any solvent can be shaken with 5 to 20 times their weight of 5% distilled water at ordinary temperature and show at least some tendency towards being self-dispersing. The solvent which is generallytried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for

, instance, parts of xylene and 20 parts of methanol,

or 70 parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a small amount of acetone to the xylene-methanol mixture, for instance, 5% to 10% of acetone. 7 V

Thepolyepoxide-treated condensates obtained in the nianrier described are, in turn, oxyalkylation-susceptible and valuable derivatives can be obtained by further reaction with ethylene oxide, propylene oxide, ethylene imine, etc.

Similarly, the polyepoxide-derived compounds can be reacted with a product having both a nitrogen group and a 1,2-epoxy group, such as 3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

Although the herein described products have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the Water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc, and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid Washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents, as, for example for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i. e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxy acetate, have sulficiently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylenesoluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a watersoluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weightof xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience what is said hereinafter will be divided into nine parts With Part 3, in turn, being divided into three subdivisions:

Part 1 is concerned with our preference in regard to the polyepoxide and particularly the diepoxide reactant;

Part 2 is concerned with certain theoretical aspects of diepoxide preparation;

Part 3, Subdivision A, is concerned with the preparation of monomeric diepoxides, including Table I;

Part 3, Subdivision B, is concerned with the preparation of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with the phenol-aldehyde resin phenol.

6 I which is subjected to modification by condensationreaction to yield the amine-modified resin;

' Part 5 is concerned with appropriate basic hydroxylated polyamines which may be employed in the preparation of the herein-described amine-modified resins;

Part 6 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which-are then subjected to reaction with polyepoxides;

:Part 7 is concerned with the reactions involving the two preceding types of materials and examples obtained 'by such reaction. Generally speaking, this involves nothing more than a reaction between 2 moles of a previously prepared amine-modified phenol-aldehyde resin condensate as described, and one mole of a polyepoxide so as to yield a new and larger resin molecule, or comparable product; I

Part 8 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products; and

'Part 9 is concerned with uses for the products herein described, either as such or after modification, includ ing any applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 As will be pointed out subsequently, the preparation of polyepoxides may include the formation at a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solvent-soluble liquids or low-melting solids. Indeed, they tend to form thermosetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from any monoepoxides and as free as possible from polyepoxides in which there are more than two epoxide groups per molecule. Thus, for practical purposes what is said hereinafter is largely limited to polyepoxides in the form of diepoxides.

As has been pointed out previously one of the reactants employed is a diepoxide reactant. It is generally obtained from phenol (hydroxybenzene) or substituted The ordinary or conventional manufacture of the epoxides usually results in the formation of a cogeneric mixture as explained subsequently. Preparation of the monomer or separation of the monomer from the remaining mass of the co-generic mixture is usually expensive. If monomers were available commercially at a low cost, or if they could be prepared without added expense for separation, our preference would be to use the monomer. Certain monomers have been prepared and described in the literature and will be referred to subsequently. However, from a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, we have found that one might as well attempt to prepare a monomer and fully recognize that there may be present, and probably invariably are present, other low molal polymers in compartively small amounts. Thus, the materials which are most apt to be used for practical reasons are either monomers with some small amounts of polymers present or mixtures which have a substantial amount of polymers present, Indeed, the mixture can be prepared free from monomers and still be satisfactory. Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher polymers.

It has been pointed out previously that the phenolic nuclei in the epoxide reactant may be directly united, or united through a variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances where the phenolic nuclei are either'u'nited directly without any intervening linking radical, or else united by a ketone residueor formaldehyde. residue. "The commercial bis-phenols available now in the open'niarke't illustrate one class: The diphenyljderivati'ves illustrate a second class, and the materials obtained by reacting substituted monofunctional phenols with an aldehyde illustrate the third class. All the various known classes may be used but our preference rests with these classes due to their availability and ease of preparation, and also due to the fact that'the cost is lower than in other examples. Y 7

Although the diepoxide reactants can 'be produced in more than one way, as pointed out elsewhere, our preference is to produce them by means of the epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds to the derivative of bis-phenol -A. It can be used'as such, or the monomer 'can be separated by an added step which involves additional expense. This compound of the following structure is preferred as the epoxide reactant and will be'used for illustration repeately with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and higher polymers are satisfactory. The formula for this compound is Reference has just been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyl-dimethyl methane, with the 4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2 isomers being present. It is immaterial which one of these isomers is used and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, to wit, Part 1, and in succeeding parts, the text is concerned almost entirely with epoxides inwhich there is no bridging radical or the bridging radical is derived from an aldehyde or a ketone. It would be immaterial if the divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere substitution of one compound for the other would be required. Thus, What is said hereinafter, although directed to one class or a few classes, applies with equal force and effect to the other classes of epoxidereactants.

' If sulfur-containing compounds are prepared they should be freed from impurities with considerable care for the reason that any time that a low-molal sulfur-containing compound can react with epichlorohydrin there may be formed a by-product in which the chlorine happened to be particularly reactive and may represent a product, or a mixture of products, which would be unusually toxic, even though in comparatively small concentration.

PART 2 Treatment with epichlorohydrin, for example, does not yield this product initially but there is an intermediate producedwhich'can be indicated by the following struc; ture: i V

Treatment with alkali, of course, forms the epoxy ring. A number of problems are involved in attempting to produce this compound free from cogeneric materials of related composition. The difficulty stems from a number of sources and a few of the more important ones are as follows:

(1) The closing of the epoxy ring involves the use of caustic sodaor the like which, in turn, is an effective catalyst in causing the ring to open in an oxyalkylation reaction.

Actually, what may happen for any one of a number of reasons is that one obtains a product in which there is only one epoxide ring and there may, as a matter of fact, be more than one hydroxyl radical as illustrated by the following compounds;

CH3 H H H t H H' H --r@i@-s-t-e o -03; 'oH'C or v I 0H, H H H H H H s@.C -st-r 0 CH: OH 011 (2) Even if one starts with the reactants in the preferred ratio, to wit, two parts of epichlorohydrin to one part of bisphenol A, they do not necessarily so react and as a result one may obtain products in which more than two epichlorohydrin residues become attached to a single bis-phenol A nucleus by virtue of the reactive hydroxyls present which enter into oxyalkylation reactions rather than ring closure reactions.

(3) As is well known, ethylene oxide in the presence of alkali, and for that matter in the complete absence of water, forms cyclic polymers. Indeed, ethylene oxide can produce a solid polymer. This same reaction can, and at times apparentlydoes, take place in connection with compounds having one, or in the present instance, two substituted oxirane rings, i e., substituted 1,2 epoxy rings. Thus, in many ways it is easier to produce a polymer, particularly a mixture of the monomer, dimer and trimer, than it is to produce the monomer alone,

(4) As has been pointed out previously, monoepoxides may be present and, indeed, are almost invariably andinevitably present when one attempts to produce polyepoxides, and particularly diepoxides. The reason is the one which has been indicated previously, together with the fact that in the ordinary course of reaction a-diepoxide, such as may react with a mole of bis-phenol A to give a monoepoxy structure. I Indeed, in the subsequent text immediately following reference is made to the dimers, trimers and tetramers in which two ep oxide groups are present. Needless to say, compounds can be formed which correspend in every respect except that one terminal epoxide group is absent and in its place is a group having one chlorine atom and one hydroxyl group, or else two hydroxyl groups, or an unreacted phenolic ring.

(5) Some reference has been made to the presence of a chlorine atom and although all effort is directed towards the elimination of any chlorine-containing molecule yet it is apparent that this is often an ideal approach rather than a practical possibility. Indeed, the same sort of reactants are sometimes employed to obtain products in which intentionally there is both an epoxide group and achlorine atom present. SeeU. S. Patent No. 2,581,464, dated January 8 1952, to Zech. v a

aging-eve {wha has been said in regard to the-theoretical aspect non-resinous to complex resinous epoxides which-are polyis, of course, closely related to the actual method of ether derivatives of polyhydric phenols containing an preparation which is discussed in greater detail in Part 3, average of more than one epoxide group per molecule and particularly subdivisions A and B. There can be no clear free from functional groups other than epoxide and hyline between the theoretical aspect and actual prepara- 5 droxyl groups. tive steps. However, in order to summarize or illustrate Referring now to what has been said previously, to what has been said in Part 1, immediately preceding referwit, compounds having both an epoxy ring or the equivaence will be made'to a typical example which already has lent and also a hydroxyl' group, one need go no further been employed for purpose of illustration. The particuthan to consider the reaction product of lar example is a r CH 3 H H H H H H H v H H H HC--C-OO COCCCH I noo-o-oOo o-c-o-on H A v H \O/ H 5H -H \O O Ha 0 It b th t t l 3 f h t 1 and bisphenol Ain amole-for-mole ratio, since the initial 3. ia a P ma f l com me reactant would yield a product having an unreacted epoxy ma 1 y W one mo 6 18']? mo ring and two reactive hydroxyl radicals. Referring again OH! to a previous formula, consider an example where two 6600 moles of bisphenol A have been reacted with 3 moles of I t13H3 epichlorohydrin. The simplest compound formed would be thus:

(Ilia EH (13H; oOo-Oo-cm- H-CHz-OO-COO (l 1;: (5H3 6H: 1113 ha a.

| 0 0 CH2 CHfl to produce the productwhich is one step further along, Such a compound is comparable to other compounds at least, towards polymerization. In other words, one having both thehydroxyl and epoxy ring such as 9,10- prior example'shows the reaction product obtained from epoxy octadecanol. The ease with which this type *of one mole of the bisphenol A and two moles of epichlorocompound polymerizes is pointed out by U. S. Patent hydrin. This product in turn would represent three moles No. 2,457,329, dated December 28, 1948, to Swern et al. of bisphenol A and four moles of epichlorohydrin. The same difiiculty which involves the tendency to For purpose of brevity, without going any further, the polymerize on the part of compounds having a reactive next formula is in essence one which, perhaps in an ideal- 40 ring and a hydroxyl radical may be illustrated by comized way, establishes the composition of resinous products pounds where, instead of the oxirane ring (1,2-epoxy ring) available under the name of Epon Resins as nowsold there is present a 1,3-epoxy ring. Such compounds are in the open market. See, also, chemical pamphlet entitled derivatives of trimethylene oxide rather than ethylene Epon Surface-Coating Resins, Shell Chemical Corporaoxide. See U. S. Patents Nos. 2,462,047 and 2,462,048, tion, New York City. The word Epon is a registered both dated February 15, 1949, to Wyler.

trademark of the Shell Chemical Corporation. At the expense of repetition of what appeared pre- CH3 H 7 I (13H. -1

H, 5H! v H H n' 7 CH3 GHQ 5 g V V I. )1; I) a CH, CH:

For the purpose of the instant invention, n may reprea viously, it may be well to recall that these materials may sent a number including zero, and at the most alow vary from simple soluble non-resinous to complex nonnumber such as 1, 2 or 3. This limitation does not exist 0 soluble resinous epoxides which are polyether derivatives in actual efiorts to obtain resins as diiferentiated from of polyhydric phenols containing an average of more than the herein described soluble materials, It is quite probable one epoxide group per molecule and free from functional that in the resinous products as marketed for coating groups other than epoxide and hydroxyl groups. The

use the value of n! is usually substantially higher. Note former are here included, but the latter, i. e., highly resinagain what has been said previously that any formula 5 ous or insoluble types, are not.

is, at best, an over-simplication, or ,at the most represents In summary then in light of what has been said, comperhaps only the more important or principal constituent pounds suitable for reaction with amines may be sum or constituents. These materials may vary from simple marized by the following formula:

11 "12 .or for greater simplicity the formula could be'restated ethers, have been described in a number of patents. For thus: a convenience, reference will be made to two only, to wit,

/O'\ I; O t o-'-o o- OR1-[R],.-R1OGC-C- -ORP[RL.R1OC-C-/EC H: H 7H: Hz (in; H2 H: H H:

in which the various characters have their prior significance and in which R 0 is the divalent radical obtained aforementioned U, patent 2,505,435, and af by the elimination of a hydroxyl hydrogen atom and a 1 tinned U S Pa,tent N 2,530,353.

nuclear hydrogen atom from the phenol 0 Purely by way of illustration, the followingdiepoxides, or diglycidyl ethers as they are sometimes termed, are OK included for purpose of illus1ration. These particular l compounds are described in the two patents just mentioned 15 t 7 TABLE I Ex- Patent ample Diphenol Dlglycldyl ether refernumber 7 once OHACJLOH), D1(epoxypropoxyphenybmethanel; 2,506,486 Di(epoxypropoxyphenyl)methylmethane 2, 506, 486 Dl(epoxypropoxyphenyl)dimethylmethane 2, 506, 486 D1(ep0xypropoxyphenyl)ethylmethylmethane 2, 506, 486 Di(ep0xypr0poxyphenyl)dlethylmethane 2,506,486 Di(epoxypropoxyphenyl;methylpropylmethane. 2, 506, 486 Di(epoxypropoxyphenyl methylphenylmethane. 2, 506, 486 Di(epoxyprop0xyphenyl) ethylphenylmethane- 2, 506, 486 Di(epoxypr0p0xyphenyl) propylphenylmethane 2, 506, 486 Di(epoxypropoxyphenyl)butylphenylmethane 2, 506, 486 (CHaCsH4)CH(CeH4OH)2 Di(epoxypropoxyphenyl)tolylmethane 2,506,486 (OHSOQH4)C(CH3)(CGHAOH)2 Dl(epoxypropoxyphenyl)tolylmethylmethane. 2,506,486 Dihydroxy dlphenyl 4,4-bls(2,3-epoxypropoxy)dlphenyl 2,530,353 (CH3)O(O4H5.C5H3OH)1 2,2-bls(4-(2,3-epoxypropoxy)2-tertiarybutyl phenyDpropane... 2, 530, 353

in which R, R", and R represent a member of the V a class consisting of hydrogen and hydrocarbon substitu- 35 Subdivision B t of the ammauc nucleus s'fud Subsmuent l As to the preparation of low-molal polymeric epoxides having not over 18 carbon atoms, n represents an integer or mixtures reference is made to numerous patents and sec lad'rereets i sg jm ffi i giz gi gg gf n n p s n particularly the aforementioned U. S. Patents Nos, 2,575,-

558 and 2,582,985. PART 3 V 40 In light of the aforementioned U. S. Patent No. 2,575 Subdivisian A 558, the following examples can be specified by reference The preparations of the diepoxy derivatives of the dito the formula therein provided one still bears in mind phenols, which are sometimes referred to as diglycidyl 1t m 65861106311 Over-Simplification- TABLE II H C'-CC OR1[R]r.R O-C-7-C- ORl'[R}nRlo'-C C C H2 H H2 H: H H,

(in which the characters have their previous signiflcence) Example R1O- from HRiOH -R-- V 'n Q n Remarks number 7 B1 Hydroxy benzene CH; 1 0,1,2 Phenol known as bis-phenol A. Low I polymeric mixture about 36 or more C where n=0, remainder largely where n=1, some where n=2. CHs

B2 do CH; 1 0,1,2 Phenol known as bis-phenolB. See note Cl3 e regarding B1 above. 3: O'Hs t B3 Orthobutylphenol 011' 1 0, l, 2 Even though n is'preferably 0, yet the usual reaction product might well contain materials where 'n is 1, or to a l lesser degree 2. H- i B4 Orthoemylphenol (7H1 1 0,1,2 Do.

B5 Orthooetylphenol EH: 1 0,1,2 Do.

B6 Orthononylphenol (311: 1' 0,1,2 Do.

"TABLE II- -Ciiiitlnued Example --R 0irom HR OH -R n n Remarks number 7 B7 OrthododeeylphenoL.-Q CH: 1 0,1,2 Even though at is preferahly 0, yet the V l usual reaction product might well con- -C .tain materials where n is 1, or to a.

] lesser degree 2. e C 3 B5: 'M'afaoresnl OH; 1 0,1,2 See prior note. This phenol used as 1 initial material 1s know'n as bis-phenol ..C O. For other suitable bis-phenols see I U. S. Patent 2,564,191. CH3 1B do CH 1 0,1,2 See prior note.

| E CH;

2810...... Dibutyl (ortho-para) phenol. 1g 1 0, 1,2 Do.

B11 Diamyl (ortho-para) phenol. EOE 1 0,1,2 Do.

B12 Dioetyl (ortho-para) phenol. 1(2)! 1 0,1,2 Do.

1313 Dinonyl (ortho-para) phenol. 161 1 0,1,2 Do.

B14.. Diamyl (ortho-para) phenol. '1 0,1,2 Do.

14 dn H 1 ,1,2 Do.

CzHs

B16 Hydroxy benzene (l) 1 0,1,2 D0.

B17 Diamyl phenol (ortho-para) -S-S 1 0,1,2 Do.

B18 do -s- 1 0,1,2 Do. 1319..., Dibutylphenol (ortho-para). g 132 1 0,1,2 Do.

' H H Ran rin H H 1 0,1,2 Do.

B21 DinonylphenoMortho-para). 1g 15 1 0,1,2 Do.

B22 Hydroxy benzene- C") 1 0,1,2 Do.

B23 do None I 0 0,1,2 DO. 1

h i l henol CH 1 0,1 2 See priornote. (As to preparation of 4 ,4- B24 on o lsopropy p l a isopropylidene bis-(Z-isopropylphenol) see U. S. Patent No. 2,482,748, dated Sept. 27, 1949, to Dietzler.) CH3 1.1. CH S-GH 1 0 1 2 See priornote. (As to preparation of the B25"- Pam 00W] phno 2- a phenol sulfide'see U. S. Patent No. 2,488,134, dated Nov. 15, 1949, to- Mikeska et a1.)

H CH 1 0 1 2 See prior note. (As to preparation'of the B26 ydmxybn'zenel a phenol sulfide see U. s. Patent No.

(lrHs i is derived from a ketone or aldehyde, particularly a g Subdivision C The prior examples have been limited largely to those in which there is no divalent linking radical, as in the case of diphenyl compounds, or here the linking radical ketone. Needless to say, the same procedure is employed in converting diphenyl into a diglycidyl ether regardless of the nature of the bond between the two phenolic nuclei. For purpose of illustration attention is directed to numerous other diphenols which can be readily converted to a suitable polyepoxide, and particularly diepoxide, reactant. r

As previously pointed out the initial phenol may be substituted, and the substituent group in turn may be a cyclic group such as the phenyl group or cyclohexyl wherein R is a member of the group consisting of alkyl,

group as in the instance of cyclohexylphenol or phenylphenol. Such substituents are usually in the ortho position and may be illustrated by a phenol of the following composition:

HO- OH Similar phenols which are monofunctional, for instance,

ditional substituent in the ortho position, may be employed in reactions previously referred to, for instance,

paraphenyl phenol or paracyclohexyl phenol with an ad- 7 with formaldehyde or sulfur chlorides to give comparable phenolic compounds having 2 hydroxyls and suitable for subsequent reaction with epichlorohydrin, etc.

Other examples include:

(In: OR1 2 CH3 CH3 H(OG2H4)9O (I)(CZHAO)BH CnHn-OCHa-UCHEM CllHll 051111 in which the C H groups are secondary amyl groups. I v w See U. S. Patent No. 2,504,064.

CoHrz CaHia See U. S. Patent No. 2,285,563.

and alkoiiy-alkyl radicals containing froml to 5 carbon atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U. S. Patent No. 2,526,545.

CH3 CH: wherein R is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R is a substituent selected from the class consisting of alkyl, cycloalkyLaryl, aralkyl, and alkaryl groups. See U. S. Patent No. 2,515,906.

CH=CH K 0H 0:02: on

HaC-Cf-CHa aC([3CHa CH: C a

See U. s. Patent No. 2,515,908.

As to sulfides the following compound is of interest:

a See U. S. Patent No. 2,331,448.

As to descriptions of various suitable phenol sulfides, reference is made to the following patents: U. S. Patents Nos. 2,246,321, 2,207,719, 2,174,248, 2,139,766, 2,244,- 021, and 2,195,539; r I

As to su1fones, see U. S. Patent No 2,122,958

As to suitable compounds obtained .by the use of 7 formaldehyde or some other aldehyde, particularly com pounds such as Alkyl Alkyl Allryl" R5 Alkyl in which R is a'methylene radical, or a substituted methderived from" formaldehyde.

ylene radical which represents the residue of an aldehyde and is preferably the unsubstitutedmethylene radical S= U. S. Patent No. 2,430,002.

See also U. S. Patent No. 2,581,919 which describes di(;dialkyl cre'sol) sulfides which include the monosulfides, the disulfides, and the .polysulfides, The following formula represents the various dicresol sulfides of this invention:

OH CH3. CH3 'QH' R2 R1 R1 R2 in which R and R are alkyl groups, the sum of whose carbon atoms equals 6 to about 20, and R and R each preferably contain 3 to about 10 carbon atoms, and x is 1 to 4. The term sulfidesas used in this text, therefore,

includes monosulfides, disulfides, and polysulfides.

PART

his well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble.

Water-insoluble resin polymers of a composition approximated in an idealized form by the formula OH OH OH OslUal R R n R In the above formula n represents a small whole number varying from 1 to 6, 7, or 8, or more, up to probably or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of the low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., It varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to carbon atoms, such as a butyl, amyl, hexyl, decyl, or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance paraphenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resins having an average molecular weightcorresponding to at least 3 and not over 6 phenolic nuclei per resin molecule. These resins are difunctional only in regard to methylol-forming reactivity, are derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol and are formed in the substantial absence of trifunctional phenols. The phenol is of the formula in which R is an aliphatic hydrocarbon radical having at least 4 carbon atoms and not more than 24 carbon atoms, and substituted in the 2,4,6 position.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic hydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

R R R .18 The basic hydroxylated amine may be designed thus:

RI HN In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the al-. dehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slightextent, if at all, 2 resin units may combine Without any amine in the reaction product, as indicated in the following formulas:

As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

in which R is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed asreactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or justv 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in TABLE III Mol. wt. Ex- Position R of resin ample R of R derived n molecule number r0m (based on n+2) Phenyl Para. 3. 992. 5

Tertiary butyl .d 3. 882. Secondary butyl. Ortho-.. 3. 882. 5 Gyclohexyl 3. 1, 025. 5 Tertiary amyl 3. 959. 5 Mixed secondary 3. 805. 5

and tertiary amyl. ropyl 3. 805. 5 Tertiary'he 3. 1, 036. 5 Octyl 3. 1, 190.5 Nonyl- 3. 1, 267. 5 Decyl- 3. 1, 344. 5 Dodecyl 3. 1, 498. 5 Tertiary'buty 3. 945. 5

Tertiary amyl. 3. 1, 022. 5 onyl 3. 1, 330. 5 Tertiary butyl 3. l, 071. 5

Tertiary amyl 3. 1, 148. 5 Non 3. l, 456. 5 Tertiary butyl. 3. 1, 008. 5

Tertiary amyl. 1, 085. 5 Non 1, 3 9? 5 V Tertiary butyl 996. G

Tertiary amyl 4. 1, 083. 4 N onyl 4. 1, 430. 6 Tertiary butyl 4. 1,094. 4 Tertiary. amyl 4. 1, 189. 6 Nonyl 4. 1, 570. 4 Tertiary amyL. 1. 604. O Oyclohexyl 1. 646. 0 Hoxyl 1. 653. 0 l. 688. 0

PART 5 As has been pointed out, the amine herein employed as a reactant is a hydroxylated basic polyamine and preferably a strongly basic polyamine having at least one secondary amino radical, free from primary amino groups, freeffrom substituted imidazoline groups, and free from substituted tetrahydropyrimidine groups, in which the hydrocarbon radicals present, whether monovalent or divalentfare. alkyl, alkylcyclic arylalkyl, or heterocyclic inv character, subject of course to the inclusion of a hy-. droxyl group attached to a carbon atom which in turn is part of a mon ovalent or divalent radical. Previous reference has been made. to a number of polyamines whichare. satisfactory for use as reactants in the instant condensation procedure. They can be obtained by hydroxylation of low cost polyamines. The. cheapest amines available are polyethylene amines and polypropylene amines. In the case of the polyethylene amines there may be as many as 5', 6 or 7 nitrogen atoms. Such aminesare susceptible to terminal alkylation or the equivalent, i. e., reactions which convert the terminal primary amino group or groups into a secondary or tertiary amine radical. In the case of polyamines having at least 3- nitrogen atorns or more, both terminal groups could be converted into tertiary groups, or one terminal group could be converted into a tertiary group and the other into a secondary amine group. In the same way, the polyamines can. be subjected to hydroxyalkylationby reaction with eth yle ne oxide, propylene oxide, glyci de, etc. In someinstances, depending on the structure, both typ es of reaction may be'employed,.i. e one type to; introduce a hydroxy ethyl group, for example and another, type to introduce a methyl or ethyl radical;

BY wa a examp e t to l wi i rm ilas re. includ: ed- It ill e noted th n p uc cl aminesln. 11. instead of being obtained from ethylene dichloride, propylene dichloride, or the like, are obtained from dichloroethyl ethers in which the, divalent radical has a carbon atom chain interrupted by an oxygen atom:

N CzBhg C nHrN H O C 2114 CaHr Another procedure for producing suitable polyamines is a reaction involving first an alkylene imine, such as ethylene imine or propylene imine, followed by an alkylene oxide, such as ethylene oxide, propylene oxide or glycide.

What has been said previously may be illustrated by reactions "involving a secondary alkylamine, or a secondary alicyclicv amine, such as dibutylamine, dibenzylamine, dicyclohexylamine, or mixed amines with an imine so as tointroduce a primary amino group which can be reacted with an alkylene oxide followed by reaction. with an imine and then the use of an alkylene oxide again. Similarly, one can start with a primary amine and introduce two moles of; an alkylene oxide so as to have a compound comparable to ethyl diethanolamine and react with two moles, of an imine and then with tWo moles of ethylene oxide.

Reactions involving the same reactants previously described, i. -e asuitablesecondary monoamine plus an alkylene imine plus an alkylene oxide, or a suitable monoamine plus an alkyleneoxide plus an alkylene imine and plus the second introduction of an. alkylene oxide, can be appliedQto a variety Qfjprimary amines. 'In the case of primary amines one can either employ two moles of an alkylene oxide so as to convert both: amino hydrogen atoms into an'alkanol group or the equivalent; or else the primary amine canjbe converted into a secondary amine by the alkylationrcaction In any event, one can obtain a series of primary amines and corresponding secondary amines which are characterized by the, fact that such aminesin'clude'groups having repetitious ether linkages and thus introduce a definite hydrophile effect by virtue of the ether linkage. Suitablepolyether amines 7 =21 susceptible to conversion in the manner .described include those of the formula in which at is a small whole number having a value of 1 or more, and may be as much as 10 or 12; n is an integer having a value of 2 to 4, inclusive; m represents the numeral 1 to 2; and m represents a number to 1, with the proviso that the sum of in plus m equals 2; and R has its prior significance, particularly as a hydrocarbon radical.

The preparation of such amines has been described in the literature and particularly in two United States patents, to wit, U. S. Nos. 2,325,514, dated July 27, 1943 to Hester, and 2,355,337 dated August 8, 1944, to Spence.

The latter patent describes typical haloalkyl ethers such as r CHg-CHQ 0 CzHsO CaH4O 021140 021140 C HACI Such haloalkyl ethers can react with ammonia, or with a primary amine such as methylamine, ethylamine, cyclohexylamine, etc., to produce a secondary amine of the kind above described, in which one of the groups attached to nitrogen is typified by R. Such haloalkyl ethers lso can be reacted with ammonia to give secondary amines as described in the first of the two patents mentioned immediately preceding. Monoamines so obtained and suitable for conversion into appropriate polyamines are exemplified by (CH OCH CH CH CH CH CH2)2NH.

Other similar secondary monoamines equally suitable for such conversion reactions in order to yield appropriate secondary amines, are those of the composition as described in U. S. Patent No. 2,375,659 dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc. 7

Other suitable secondary amines which can be converted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No. 2,482,546 dated September 20, 1949, toKaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta phenoxyethylamine, gamma phenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and beta-phenoxypropylamine.

Other secondary monoamines suitable for conversion into polyamines are the kind described in British Patent No. 456,517, and may be illustrated by with the statement that such presentation is an oversimplification. It was pointed out that at least one occurrence of R' must include a secondary amino radical of the kind specified. Actually, if the polyamine radical contains two or more secondary amino groups the amine may be reactive at two diiferent positions and thus the same amine may yield compounds in which R and R are dissimilar.

CH3 7 H NpropyleneNpropyleneN CH3 CH8 NCZH-tNGflH4NC2 4 2 4 H H H HO 03H; CzHgOH In the first of the two above formulas if the reaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylenebridge, would be different than if the reaction took place at the intermediate secondary amino radical as differentiated from the terminal group. Again, referring to the second formula above, although a terminal amino radical is not involved it is obvious again that one could obtain two difierent structures for the radicals attached to the nitrogen atom united to the methylene bridge, depending on wheher the reaction took place at either one of the two outer secondary amino groups, or at the central secondary amino group. If there are two points of reactivity towards formaldehyde as illustrated by the above examples it is obvious that one might get a mixture in which in part the reaction took place at one point and in part at another point. Indeed, there are well known suitable polyamine reactions where a large variety of compounds might be obtained due to such multiplicity of reactive radicals. This can be illustrated by the following formula:

Certain hydroxylated polyamines which may be employed and which illustrate the appropriate type of reactant used for the instant condensation reaction may be illustrated by the following additional examples:

N-oH2oH2N-omomo11 HOCHzCHzNH-OH2OHn-NHOHzOHzOH on I OH HOCHQOH0HzNH-CHzOHz-NHCHzOHCHzOH HoornomNH-om HOOH2OHzNH-CH HoomomNH- Hi As is well known one can prepare ether amino alcohols of the type in which R represents analkyl group varying from methyl to normal decyl, and in fact, the group may contain as many as 15, 20 or even 30 carbon atoms. See J. Org. Chem, 17, 2 (1952).

ver and above the specific examples which have appeared previously, attention is directed to the fact that a number of suitable amines are included in subsequent Table IV.

PART 6 The products obtained by the herein described processes represent cogeneric mixtures which are the result. of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is diflicult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds'to. somewhat similar derivatives made either frornphenols as differentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else frorn a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heatreactive resin. Since the condensation products obtained are not heat-convertible and since 'manufacture is not restricted to a single phase system, and since temperatures up to 150 C. or thereabouts may be employed, it is obvious that the procedure becomes. comparatively simple. Indeed, perhaps no description: is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No.- 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed assubsequently described; in fact, usually it is apt tobe a solid at distinctly higher temperatures, for instance, or,dinary room temperature. Thus, We have found it convenient to use asolvent and particularly one which can be removed readily'at a comparatively master "2.4 moderate temperature, for instance, at C; A suitable solvent is'usually benzene; xylene. or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction,

and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively nonvolatile solvent such as dioxane or the diethylether of ethyleneglycol. or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in any oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction. 7

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. 'H'owever, paraformaldehyde can be used but it is more ditficult perhaps to add a solid material instead of the liquidsolut-ion and, everything else being equal, the latter is apt to be more economical. In any event, water ispresent as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the, material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction Where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

Another factor, as far asthe selection of solvent goes, is whether or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt to be solids or thick viscous liquids in which there is some change from the initial resin itself, particularly if some of the initial solvent is apt to remain without complete removal, Even, if one startswith a resin which is almost invariably a dark red in color or at least a red-amber, or some color which includes both an amber component and a reddish component. is apt to be lower and the products may be more sticky and more tacky than the original resin itself. Depending on the resin selected and, on. the amine selected the condensation product or reaction-mass on a solvent-free basis may be hard, resinous and comparable to the resin itself.

The products obtained, depending on the. reactants selected, may be Water-insoluble or water-dispersible, or water-soluble, or close to being Water-soluble. solubility is enhanced, of. course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. Gne also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any water present by refluxing with benzene or the'like. In

" fact, the selection of the solvent employed may depend in part whether or not. the. product at the completion of the reaction is to be converted into a salt form.

In the next succeeding-paragraph it is pointed out that,

frequently it is convenient to eliminate all solvent, using a temperature of not over 150 C. and employing vacuum, if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can

beusedi' The selection of solvent, such as benzene,

One can also use a mixture of benzene By and large, the melting point Water 25 .s xylene, or the like, depends primarily on-oost, i. e., the use 'of the most econ'omical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal? (b) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylation?; and the third factor is this, (c) is an effort to be made to purify the reaction mass by the usual procedure as, for example, a water-wash to remove any unreacted water-soluble polyamine, if employed and present after reaction? Such procedures are Well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, we have found xylene the most satisfactory solvent.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. We have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. venience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added, preferably in a powdered form, is completely soluble. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the polyamine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a threephase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons-pointed out we prefer to use a solution and whether to use a commercial This, again, is a matter of con- 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale if there is any difficulty with formaldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difficulties are involved. We have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method-of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as far as one can'reasonablyexpect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C., for 4 or 5 hours, or at the most, up to 10-24 hours, we then complete the reaction by raising the temperature up to 150 C., or thereabouts' as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature we use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about C., and generally slightly above 100 C., and below C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted ina conventional manner in the same ,way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary polyamine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases We have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible We have. checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the end-product showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted polyamine, if any is present, is another index.

In light of what has been said previously little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 1b The phenol-aldehyde resin is the one that has been identified previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The mo- 75 lecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei as the value for n which excludes the 2 external nuclei, i. e.,' theresin was largelya mixture havingfi nuclei and 4 nuclei,

28 thereabouts. Usually the: mixture yielded a clear solution by the time'the bulk of thewater, or all of the water, had been removed. a I i Note that as pointed out previously, this procedure is excluding the 2 external nuclei, or 5 and 6 overall nuclei. 55 illustrated by 24 examples. in Table e s s TABLE IV Strength of Reac- Reec- Max. Ex. Resin Amt., Amine used and amount tormalde- Solvent used tlon tlon distill. N d g 7 hyde soln. and amt. temn, e, temp.,

" and amt. I hrs. 0.

30%, 200 g-.- Xylene, 600 g- 21-24 24 150 37%, 81 g Xylene, 480 g. -23 27 156 do Xylene, 610 g. 22-27 25 142' Xylene, 300 g 28 145.

Xylene, 425g "34 150 V Xylene, 500 g 152 882 Amine O, 324 g Xylene, 625 g 38 141- 480 Amine O, 162 g..- Xylene, 315 g 20=-2l 25 143 473 Amine D, 256 g Xylene, 425 2.... 22-25 25 148 do Xylene. 450 g 20-21 25 p 158,-

Xylene, 525 'g 21-25 28 152.

Xylene, 400 g 22-24 26 143 Xylene, 500 g 26-27 34 1 141 Xylene, 400 g 21-23 25 153- Xylene, 500 g 23-25 27 155' Xylene, 400 g.... 20-21' 34 150.

Xylene, 450 g 20-24 36 152 Xylene, 500 g 20-22 30 148 Xylene, 400 g 20-29 24 143 ;.do Xylene, 450 g 20-22 32 151 391 Amine I, 86 g-- 30%, 50 g Xylene, 300 15.... 20-26 36 147 The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a preceding, were powdered and mixed with a considerably lesser weight of xylene, to wit, 500 grams. The mixture was refluxed until solution was complete. It was then adjusted to 'approxi-' mately 33 to 38 C., and 296 grams of symmetrical di(hydroxyethyl)ethylenediamine were added. The mix-- ture was stirred vigorously and formaldehyde used was a 30% solution and the amount employed was 200 grams.

It was added in a little over 3 hours. The mixture was stirred vigorously and kept within a temperature range of 33 to 48 C. for about 17 hours. At the end of this time it was refluxed using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of formaldehyde was noted. Any unreacted formaldehyde seemed to disappear within about 3 hours or thereabouts. As soon as the odor of formaldehyde was no longer particularly noticeable or detectible the phase-separating trap was set so as to eliminate all the water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately 150 C. or perhaps a little higher. The reaction mass was kept at this temperature for a little over 4 hours and the reaction stopped. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene. The residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for reaction was somewhat under 30 hours. .In other examples it varied from 24. to more than 36 hours. The time can be reduced by cutting the low temperature period to approximately 3 to 6. hours. Note that in- TableIV followingthere are a large number. of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared; 'After theodor of formaldehyde disappeared the phase-separating trap was employed to separate out all the-water, both the solution and condensation. After all the water had been separated enough xylene was takenout to have the final product reflux for s'everah hours somewherein the range of 145 to 150 C'., or

As to the formulas of the above amines referred to as Amine A through Amine I, inclusive, see, immediately following:

Amine H- no omomNH-o H,

HOCH:CHaNH H noomomNH- n. Amine 1- oHrNHoH,

CHaNHom-omorr' V onzNncm A 7 PART 7 The productsobtained as herein described by reactions involving amine condensates and diglycidyl ethers orthe. equivalent are valuable for use as such. ispointed out in. detail elsewhere- However, in many instances the derivatives, obtained. by oxyalkylation are even more valuable and fromsuchstandpointthefhereiri described products may be. 'consideredias 'valua,ble,' -in-, termediates. Subsequent oxyalkylation involves the use:

of ethylene oxide, propylene oxide, bntyl'ene oxide, glyas differentiated from polyepoxides.

It becomes apparent that if the product obtained is to be treated subsequently with a monoepoxide which may densate 2b. Condensate 2b was obtained from resin 5a. Resin 6a was obtained from tertiary amylphenol and formaldehyde. The amount of resin employed was 480 grams. The amount of amine employed (Amine A) require a pressure vessel as in the case of ethylene x was 148 grams. The amount of 37% formaldehyde emide, it is convenient to use the same reaction vessel in ployed was 81 grams. The amount of solvent employed both instances. In other words, the 2 moles of the amine was 480 grams. Amine A, as previously indicated at the modified phenol-aldehyde resin condensate would be re end of Table IV, preceding, was symmetrical di(hydroxyacted with a polyepoxide and then subsequently with a ethyl)ethylene diamine. All this has been described monoepoxide. In any event, if desired the polyepoxide 10 previously. reaction can be conducted in an ordinary reaction vessel, The solution of the condensate in xylene was adjusted c a the usual glass laboratory equipment s i to a 50%, concentration. In this particular instance, particularly true of the kind used for resin manufacture d i practically all th the whi h a pear i th 88 described in a number of Patents, as eXamPIe, subsequent table, the examples are characterized by the Patent No. 2,499,365. fact that no alkaline catalyst was added. The reasonis, cognizance Should be taken of one Particular feature of course, that the condensate as such is strongly basic. in Connection With the 1'eaetioh involving the p y p x If desired, a small amount of alkaline catalyst could be nd that is this; the amine-modified phenol-aldehyde resin added, such as finely powdered caustic soda, sodium condensate is invariably basic and thus one need not add methylate, If Such l i a l i added it may the usual catalysts which e Used t0 E Such speed up the reaction but it also may cause an undesiro Generally p the reaction W111 Proceed able reaction, such as the polymerization of the diepoxide. at a satisfactory rate under suitable conditions without In any eveht, 12 grams f the condensate were y ye at solved in approximately an equal weight of xylene and p y Polyepoxldes combmahon h anon stirred and heated to 100 C. 17 grams of the diepoxide basic reactant the usual catalysts include alkahne matepreviously id tifi d as 3 A, and dissolved in an equal rials Such as eahstle soda, eaustle P e hs eodlum meth' weight of xylene, were added dropwise. The initial y Qthef Catalyst? y e aeldle lhhatul'e e addition of the xylene solution carried the temperature are of the kind characterized by iron and tin chloride. above 109 The remainder of the diepoxide was added Furthermore, insoluble catalysts such as clays or spein about an'hours time During this period f time eially preparedmineral catalysts have been used- If for the temperature rose somewhere above 120 C. The 'f reasonflm Faction did not Proceed rapidly enough product was allowed to reflux at about 130 C., using a with the diglycidyl ether or other analogous reactant, phase separating trap A small amount of Xylene was then ;a small amount of finely divided caustic soda or removed by means of the phase separating trap as 1the fF methylate could be employed as a catalyst The temperature gradually rose to 170 C. or slightly less. i genfirauy emhloyed would be or The mixture was then refluxed at about this same tem- Q wlthout Saying that the can take i perature for about 4 or 5 hours until the reaction had an 9 solvent oxyalkylatloxi' stopped and the xylene which had been separated out susfepuble Gel-Frau? fi thls i more fiyi during the reflux period, was returned to the mixture. fi z i g i zgf g g as 53 32: 3 f f g 40 The overall reaction time was about 7 hours. A small g f z g from a egroleum g one amount of material was withdrawn and the xylene evapp orated on a, hot plate in order to examine thephysical employ an oxygenated solvent such as the diethylether of properties. The materlal was a dark red viscous semiethylene glycol or the dlethylether of Propylene glycol solid It was insoluble in water it was insoluble in a 5% or similar ethers, either alone or in combination with a l d 1 bl 1 d hydrocarbon solvent. The selection of the solvent deg ucfmlc so i an 1 was so u m Xy an pends in part on the subsequent use of the derivatives partlcularly m a mlxtlire of 80 paits Xy and 20 Parts or reaction products. If the reaction products are to be methanql' However 1f the.-matenal W dlssolved m rendered solvent-free and it is necessary that the solvent he Solvent then shaken i 5 glucomc be readily removed as, forexampleyby the use of acid it showed a definite tendency to disperse, suspend, uum distillation, thus xylene or an aromatic petroleum or form a 501 e pamculalrly 'ilxylenefmethanol mlxed will serve If the product is going to be subjected to solvent as previously described, with orwithout the further oxyalkylation subsequently, then the solvent should be addmon ofahtfle acetone one which is not oxyalkylation-susceptbile. It is easy The Y 1S slmPle m hght of enough to select a suitable solvent if required in any inf f has been Sald PICWOPSIY and m effect a Pmcedure stance but, everything else being equal, the solvent chosen 5 slmllal' to that p y In the use of glyelde y sheuld b the most economical one glycide as oxyalkylating agents. See, for example Part 1 1 of U. S. Patent No. 2,602,062 dated July 1, 1952, to Exam? 8 De Groote.

The product was obtained by reaction between the di- Various examples obtained in substantially the same epoxide previously designated as diepoxide 3A, and conmanner are enumerated in the following tables:

TABLE V,

0011- Time Ex. den- Amt, Diep- Amt., Xylene, Molar of reac- Max. No. sate grs. oxide g'rs. grs. ratio tion, temp, Color and physical state used used hrs. 0.

ML... 123 3A 17 2:1 7 170 Dark semi-solid. 2o- 134 3A 17 2:1 8 168 Do. a 123 3A 17 140 2:1 7 175 D0. 40--.- 130 3A 17 147 2:1 7 172 Do. 50--.. 148 3A 17 an s 168 Do. 60 187 3A 17 .204 2:1 8 175 Dark solid mass. 70---. 132 3A 17 150 2:1 8 168 Do. so-- 12b 152 3A 17 2:1 8 170 Do. 90---- 19b 136 3A 17. 153 an s 165 Do. 100..- 20b 145 3A 17 162 2:1 8 170 Do.

TABLE VI Con- 'Ilme Ex. den- Amt, Dlep- Amt., Xylene, Molar of reac- Max; No. sate grs. oxide grs. grs. ratio on, temp, Color and physical state used used hrs. 0. I

1D 128 B1 27. 166 2:1 7 165 Dark semi-solid. 2D.. 134 B1 27.5 162 2:1 7 170 Do. 3D 123 B1 27. 5 150, 2:1 7 V 170 Do. 4D 130 B1 27.5 153 2:1 7 175 Do. 5D 148 B1 27. 5 176 2:1 3 172 Do. 6D 187 B1 27. 6 215 2:1 8 168 Dark solid mass. 7D 132 B1 27. 5 160 2: 1 7 170 Do. 8D. 152 B1 27. 5 180 2: 1 8 176 D0. 9D 136 B1 27. 5 164 2:1 8 V 165 Do. 10D--- 145 B1 27. 5 173 2:1, 8 180 Do.

Solubrhty 1n regard to all these compounds was substan- 5 the theoretical amount of dlepoxlde, for instance, 90%- tially similar to that which was described in Example 1C.

TABLE VII Probable Probable Resin conmol. wt. of Amt. of Amt. of number of Ex, No. densate reaction product, solvent, hydroxyls used product grs. grs. per molecule TABLE VIII Probable Probable Resin conmol. wt. of Amt. of Amt. 01' number of Ex. No. densate reaction product, solvent, bydroxyls used product grs grs. per molecule At this point it may be desirable to direct attention to two' facts, the first being that we are aware that other diepoxides free from an aromatic radical as, for example, epoxides derived from ethylene glycol, glycerine, or the like, such as the following:

may be employed. to. replace'the diepoxides herein de-. scribed. However, such derivatives are not included as part of the instant invention.

Attimes we have found a tendency for aninsolublefmass to form or at least to obtain incipient crosslinking or gelling even when the molal' ratio is in order of 2 moles 'of resin to one of diepoxide. We have foundthis can be avoided by anyone of the. iollowinglprocedures, or their equivalent. with an inert solvent, such as xylene or the like. In: some instances an oxygenated solvent, such as the diethyL ether of ethyleneglycol may be employed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the temperature of reaction by adding a small amount of initially lower boiling :solvent such as benzene, or use benzene entirely. Also, we havenf ound it desirable at times to use slightly less than apparently Dilute the resin or the diepoxide, or. both,

to instead of The reason for this fact may reside in the possibility that the molecular weight dimensions on either the resin molecule or the diepoxide molecule may actually vary from the true molecular weight by several per cent. 7

Previously the condensate has been depicted in a simplified form which, for convenience, may be shown thus:

(Amine) CH (Resin) CH (Amine) Following such simplification the reaction product with a p-olyepoxide and particularly a diepoxide, would bein-' dicated thus: a

[(Amine) C H;(Resin) C H:(Amine)] (Amine) C H: (Resin) C Hz (Amine) in which D. G. E. represents a diglycidyl ether as specified. If the amine happened to have more than one reactive hydrogen, as in the case of a hydroxylated' amine or po1y amine, having a multiplicity of secondary amino groups it is obvious that other side reactions could take place as indicated by the following formulas:

[(Amine) CH, (Amine) D. G. .E.

[(Amine) CH2 (Amine) [(Resln) CH;(Resln)] i V D. G. E. [(nesmcnunesm] treatment of oilfield emulsionsare used as such, or after dilution with any suitable solvent, such as water,

"petroleum hydrocarbons, such as benzene, toluene, V, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols,

particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with'one or more of 'the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, soluble form, or in a form exhibiting both oiland watersolubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of l to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such as apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials of our invention when employed as demulsifying agents.

The materials of our invention, when employed as treating or demulsifying agents, are used in the conventional way, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part Three, and reference is made thereto for a description of conventional procedures of demulsifying, continuous, and down-the-hold demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

The product of the present invention, for example, the product of Example 1C, 20%; V

A cyclohexylamine salt of a polypropylated monosulfonic acid, 24%; V

An ammonium salt of a polypropylated napthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%; 7

A high-boiling aromatic petroleum solvent, Isopropyl alcohol, 5%.

v The above proportions are all weight percents. 7

PART 9 The products herein described as such and prepared in accordance with this invention can be used as emulsifying agents, for oils, fats and waxes, as ingredients in insecticide compositions, or as detergents and wetting agents in the laundering, scouring, dyeing, tanning and mordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes. I

Other uses include the preparation or resolution of petroleum emulsions, whether of the water-in-oil type or oil-in-water type. They may be used, as additives in connection with other emulsifying agents; they may be employed to contribute hydrotropic efiects; they may be used as anti-strippers in connection with asphalts; they may be used to prevent corrosion, particularly the corrosion of ferrous metals for various purposes and particularly in connection with the production of oil and gas, and also in refineries where crude oil is converted into various commercial products. The products may be used industrially to inhibit or stop micro-organic growth or other objectionable lower forms of life, such as the growth of algae or the like; they may be used to inhibit the growth of bacteria, molds, etc.; they are valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils, and also to hydraulic brake fluids of the aqueous or nonaqueous type, some have definite anti-corrosive action. They may be used also in cnnnectionwith other processes where they are iniected into an oil or gas well for purpose of removor in an oilincluding batch,

napthalene 32 carbon atoms.

7 34v ing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondaryrecovery operations using aqueous flood waters. They can also be used in dry cleaners soaps.

With regard to the above statements, reference is made particularly to the use of the materials as such, or in the form of a salt; the salt form refers to a salt involving either one or both basic nitrogen atoms. Obviously, the salt form involves a modification in which the hydrophile character can be either increased or decreased and, inversely, the hydrophobe character can be decreased or increased. For example, neutralizing the product with practically any low molal acid, such as acetic acid, hydroxyacetic acid, lactic acid, or nitric acid, is apt to markedly increase the hydrophile effect. One may also use acids of the type in whichR is a comparatively small alkyl radical,such as methyl, ethyl or propyl. The hydrophile effect may be decreased and the hydrophobe effect increased by neutralization with, amonocarboxy detergent-forming acid. These are acids which have at least 8 and not more than .They are obtained from higher fatty acids and include also resin acids such as abietic acid, and petroleumacids such as naphthenic acids and acids obtained by the oxidation of wax. One can also obtain new products having unique properties by combination with polybasic acids, such as diglycolic acid, oxalic acid, dimerized acids from linseed oil, etc. The most common examples, of course, are the higher fatty acids having generally 10 to 18 carbon atoms. We have found that a particularly valuable anti-corrosive agent can be' obtained from any suitable resin and formaldehyde provided the secondary amine is dicyclohexylamine. The corrosion-inhibiting properties of this compound can be increased by neutralization with either one or two moles of an oil-soluble sulfonic acid, particularly a sulfonic acid of the type known as mahogany sulfonic acid.

The oil-soluble sulfonic acids previously-referred to may be synthetically derived by sulfonating olefins, aliphatic fatty acids, or their esters, alkylated aromatics or their hydroxyl derivatives, partially hydrogenated aromatics, etc. With sulfuric acid or other sulfonating agents. However, the soaps of so-called mahogany acids which are usually produced during treatment of lubricating oil distillates with concentrated sulfuric acid or higher concentration) remain in the oil after settling out sludge. These sulfonic acids may be represented as where (R), is one or more alkyl, alkaryl or aralkyl groups and the aromatic nucleus may be a single or condensed ring or a partially hydrogenated ring. The lower molecular weight acids can be extracted from the acid treated oil by adding a small amount of water, preferably after dilution of the oil with kerosene. However, the more desirable high molecular Weight (350-500) acids, particularly those produced when treating petroleum distillates with fuming acid to produce white oil, are normally recovered as sodium soaps by neutralizing the acid oil with sodium hydroxide or carbonate and extracting with aqueous alcohol. The crude soap extract is first recovered as a water curd after removal of alcohol by distillation and a gravity separation of some of the contaminating salts (sodium carbonate sulfates and sulfites). These materials still contain considerable quantities of salts and consequently are normally purified by addition of a more concentrated alcohol followed by storage to permit settling of salt brine. The alcohol and water are then stripped out and the sodium salts so obtained converted into free acids.

. Not only can one obtain by-product sulfonic acids of the mahogany type which are perfectly satisfactory and enhanced in comparison with the resin as such. A proceduredesigned primarily to enhance the hydrophobe properties of the resin involvestderivatives obtained by a phenyl or substituted phenyl glycidyl ether, of the structure. i p V in which 'R represents a hydrocarbon substituent such as an alkyl radical having 1 to 24 carbon atoms, or a cyclic group, such as a cyclohexyl group, a phenyl group, or a benzyl group, and n represents -0,' l, 2.0r 3. vr1 is zero in the instance of the unsubstituted phenyl radical, Such compounds are in essence oxyalkylating-agents and reac'tioninvolvesthe introduction of a hydrophobetgroup and the formation of an jalkanol hydroxyl radical.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i. e., combination of water or particularly in the formtof a low molal organic acid such as the acetate or hydroxyacetate, have snfiiciently hydrophile character to at least meet the test set forth, in UMS. Patent No. 2,499,368, dated March 7, 1950, to De Groo'te et al. In said patent such test foremulsification using a water-insoluble sol vent, generally Xylene, is described as an index of surface activity.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. The method of (A) condensing (a) an oxyalkylanon-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, l0W-stage phenol-aldehyde resin having an average molecular Weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula temperature suificiently high "to eliminate water. and

below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that'the resinous con-j densation product resulting from the process be .heatstable and oxyalkyladon-susceptible; 'followed by 1(B') reacting said resin condensate with a phenolic polyepoxide containing atleast 1,2-epoxy rings. and being free from-reactive functional groups other than 1,2-epoxy and hydroxyl groups and cogenerically associated compounds formed in the preparation of saidjpolyepoxides; said epoxides being monomers and'low molal polymers not exceeding the tetramers; said polyepoxides being ,selected from the class consisting .of ;(a a,) compounds where the phenolic nuclei are directly joined without an intervening'bridge radical, and -(b b compounds contain-' ing a radical in whichf2 phenolicnuclei are joined by a divalent radical selected from the class consisting of ketone residues formed by theselimination of the 'ketonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehyde oxygen atom, thefdivalent ad al 7 -13 ,H

V n H V the divalent V V or II C radical, the divalent sulfone radical, and thedivalent monosulfide radical S the divalent radical CH SCH and the divalentdisulfide radical -S-S-; said phenolic portion-of the diepoxide being obtained from a phenol of the structure in which R, R", and R' represent a member of. the class consisting of hydrogen and hydrocarbon substituents 'of the aromatic nucleus, .said substituent member having not over, 18 carbon atoms; with the 'further 'pro-' viso that said reactive compounds (A) and '(B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the added proviso that the reactionproduct be a member of the class of solvent-soluble liquids and low-melting solids; said reaction between (A) and (B) being conducted below the'pyrolytic point of the reactants and the resultants of reaction; andtwith thelfinal proviso that the ratio of reactants be approximately 2 moles of the, resin condensate per mole, of the phenolic polyepoxide.

2.]The method of, (A) condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organiclsolventsoluble water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least Sand not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in fregardto .methylole forming reactivity; said resin being derived by reaction betweena difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said r'esin'being formed in the substantial absence of trifunctional phenols; said phenol being of the formula 'stituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature-sutficientty high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting .from the process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting a phenolic diepoxide free from reactive functional groups other than 1,2-epoxy and hydroxy groups, and cogenerically associated compounds formed in the preparation of said diepoxides; said epoxides being selected from the class consisting of (aa) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (bb) compounds containing a radical in which 2 phenolic nuclei are joined by a divalent radical the divalent ll radical, the divalent sulfone radical, and the divalent monosulfide radical -S, the divalent radical CH SCH and the divalent disulfide radical --S-S-; said phenolic portion of the diepoxide being obtained from a phenol of the structure in which R, R", and R'" represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; the molar ratio of reactant (A) to reactant (B) being approximately 2 to 1 respectively; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of solventsoluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

3. The method of (A) condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 .and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aidehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrirnidine radical; and (0) formaldehyde said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting fromthe process be heatstable and oxyalkylation-susceptible; followed by (B) reacting a member of the class consisting of (aa) compounds ot the following formula in which R represents a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom and aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical H H C C H u the divalent radical, "the divalent sulfone radical, and the divalent monosulfide radical -S-, the divalent radical- -CH SCH and the divalent disulfide radical SS-; and R 0 is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol.

in which R, R", and R represent a member of the class consisting of hydrogen and hydrocarbon substituents oi the aromatic nucleus, said substituent member having not over 18 carbon atoms; n represents an integer reaction product be a member of the class of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and resultants of reaction.

' 4. The method of (A) condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional' monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at temperature sufficiently high toeliminatewater'and'below the pyrolytic point .of the reactants and resultants of reaction; andwith the proviso that the resinous condensation product resulting from-the process be heat-stable and amine having. at least one secondary amino group and havingnotoverf32. carbonatoms in any radicalattached to any amino nitrogen atom, and with'jthe further provisoj that the polyaminebe free from :any primary amino oXyalkylation-susceptible; followed by (B) reacting a following formula memberof .theclass consisting of (ca .compounds .of the wherein R is an aliphatic hydrocarbon bridge, each n in-' dependently has one of the values to 1, and'R is an alkyl radical containing from .1 to 12 carbon atoms, and (bb) cogenerically associated'compounds formed in the preparation of (aa) preceding, including monoepoirides; with the proviso that (B) consist principally of the monomer as distinguished from other cogeners; the molar ratio of reactant (A) to reactant "(B) being approximately 2 to 1 respectively; with the further proviso that said reactive compounds (A) and (B) be members' of the class consisting of non-thermosetting organic solventsoluble liquids andlow-melting solids; with the final proviso that the'reaction'product be-a memberof the class of solvent-soluble liquids and flow-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

5. The method of (A) condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least3 and not over' 6 phenolic nuclei per resin molecule; said resin being difunctional only in;regard to methylolforming reactivity; said resin being :derived by reaction between a difnnctional monohydric phenol and an aldehyde having not over8 carbon atoms and reactive toward said phenol; 'said resin being formed in theisubstantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6-position; (b) a basic hydroxylated polyradical, any substitutedimidazoline radical and "any 'sub stitut ed.tetrahydropyriniidine radical; and .(c) formaldehyde; said condensationreaction being conducted at a temperature sufiiciently high :to'eliminatewater and below the pyrolytic point of the reactants and resultants of reaction; and with theprovisosthat the resinous condensation pro'tiuctrcsultingfrom the process be "heat-stableand oxyalkylation-susceptible; followed by (B) reacting a (an) compounds of "the member of the class-consisting of following formula:

and (bb) cogenerically' assoeiated'compounds formed in the preparation of (aa) preceding, includingm'onoepoxides; with the proviso that (B) consist principally of the monomer asdistinguished fromother' cogeners; the m'olar ratio of reactant (A) to reactant (B) being approximately 2 to 1 respectively with" the further proviso that said reactive compounds (A) a'nd'(B) be membersof the class consisting of non-thermosetting organic solventsoluble liquids and low-melting solids; with the final proviso that the reaction producLbe a member of the class ofoxyalkylationand acylation-susceptible.solyent-soluble liquids and lowemelt'ing solids; and said. reaction between (A). and (B) being conducted below the pyrolytic point of the reactants and the resultants vof reaction.

' 6. The method of claim 11' wherein the precursory phenol contains at least 4*and not over14 carbon atoms in the substituent radical.

7. 'The method of claim 1 wherein the precursory phenol contains at least 4 and not over 14 carbon atoms in the substituent radical andwthe precursory aldehyde is formaldehyde.

,8. The product obtained .bythemethod described in 7 References Cited'in the file of this patent 5 UNITED STATES PATENTS Greenlee Sept. 12, 1950 De .Groote Apr. 24, 1956 

1. THE METHOD OF (A) CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENTSOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOLFORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 